Vinyl chloride resin plasticized with tris (tetrahydrofurfuryl) (1&#39;, 2&#39;-dicarboxyethyl) octadecenoate



acids or anhydrides with :tives.

byClocker in U. Finclusive. "enic acids of not more than 6 carbon atoms combined at a carbon of the carbon atom chain of a non-conjugated, aunsaturated, non-hydroxylated fatty acid having from 10 linoleic acid, linolenic acid, etc.

V INYL CHLORIDE RESlN PLASTICIZED WITH T R I S (TETRAHYDROFURFURYL). (1,2' DICAR- BOXYETH-YL) OCTADECENOATE Ohio, assignor to Monsanto Joachim TDazzi, 'Dayton, G M0,, a corporation or Chemical Company, St. Louis, Delaware 'No'Drawing. Application February 9, 1956,

SerialNo. 564,357

1 Claim. (Cl. 260-23) 'Thisinvention relates to heterocyclic derivatives of adducts formed by the addition reaction of u,;3-ethylenic certain higher fatty acids, and "to vinyl'chloride polymers plasticized with such deriva- The preparation of adducts by reaction of an (1,5-

:ethylenic acid or anhydride with an unsaturated, nontconjugated, non-hydroxylated fatty acid containing from IO to 24 carbon atoms in its carbon chain is described S. Patents Nos. 2,188,882 to 2,188,890, The adducts are polybasic, acyclic, afi-fithyl- :to 24 carbon atoms or an ester thereof. Suitable 00,]3- tethylenic acids or anhydrides for use in the preparation at the adducts are maleic anhydride, maleic acid, fumaric :acid, citraconic acid, citraconic anhydride, etc. Suitable 'fatty acids for use in the addition reaction with the above ot,; -ethylenic compounds for the preparation of the adtducts-include oleic acid, undecylenic acid, elaidic acid, ForIthe sake of brevity and convenience, the addition products obtained by reaction of an a,fl-ethylenic acid or anhydride with a nonconjugated unsaturated, non-hydroxylated fatty acid or fatty acid ester will be hereinafter referred to as Clocker adducts.

I have found that highly valuable derivatives are obtained by reacting tetrahydrofurfuryl alcohol with the Clocker adductof maleic anhydride and a non-conjugated, non-hydroxylated aliphatic olefinic acid of from it) to 24 carbon'atoms or an alkyl ester of said acid. Thus, the adduct of maleic anhydride with a fatty acid or an ester thereof such as octadecenoic acid or an alkyl octadecenoate'having the probable structure:

0113mm),oHoH;CH(OH2)n-,oo01t H--C=O in which R is a member of .the' group consisting of hydrogen and alkyl groups of from 1 to is a whole number of from 8 carbon atoms and x S to 8,is-contacted with tetrahydrofurfuryl alcohol in the presence of an esteri- 1 :fyingcatalyst to yield the triester:

in which Z is the tetrahydrofurfuryl radical, x is a whole number' offrom to 8 carbon atoms, and Y is a member of Z and alkyl groups: of from of the group consisting Theuesters of (1.',2-dicarboxy- 1",2' biscarboxymethyl) octarnixed: esters in which only the the tetrahydrofurfuryl alcohol,

.tageously employed as plasticizers 2,809,947 Patented Oct. 15, 1 957 "ice 7 2 maleic group is vesterified by the tetrahydrofurfuryl alcohol, e. g., n-butyl 1,2'-bis(carbotetrahydrofurfuryh oxy)octadecenoate. The'mixed estersmay be obtained by employing in the esterifyingstep an adduct of maleic anhydride and analkyl ester of a non-conjugated, un= saturated non-hydroxylated fatty acid. Because of un= certainty concerning the position at whichthe maleic residue isattached to the fatty acid, the present esterswill be hereinafter referred to without specifically indicating the position of the (1',2-dicarboxyethyl) group.

Esterifying catalysts of general utility in the prepara tion of the present esters are acidic or basic-materials for example, p-toluenesulfonic acid; sulfuric acid, pyrophosphoric acid, hydrochloric acid, sodium ,methylate, etc. Reaction of the Clocker-adducts with the present tetrahydrofurfuryl alcohol occurs to some-extent at ordinary room temperature; however, in orderto obtain good yields it is preferredto heat the reaction mixture, advantageously at refluxing temperatures. Inasmuch as the esterification reaction involves the condensation of one mole of the Clockeradduct with from two to three moles of depending upon whether theadduct is a free acidor a mono-esteryit is preferred to employ stoichiometric proportions-of the reactants. However, since any excess of eitherthe Clockeradduct -or the tetrahydrofurfuryl alcoholmay be readily recovered from the final product, the quantity of reactants employed in the. initial reaction mixture is immaterial. It is preferred, however, to use an excess of the alcohol in order to minimize incomplete esterification.

:The present estersqof the Clocker adducts are stable, high boiling, viscousproducts which are very advan- V forpolyvinyl chloride. Adducts of. acyclic -olefinic acids and, long-chained unsaturated. acids have.been hitherto generally suggested for use as softening agents. I have now found that of outstanding value as plasticizers for vinyl chloride polymers are esters prepared as described above and having the formula:

r-ooor one o o z H2COOVZ carbon atoms, Zis the tetrahydrofurfuryl radical and. Y

is selected from the class consisting of the-tetrahydrofurfuryl radical and an alkylradicalof from 1 to 8 carbon atoms. These esters, serve, not only to soften vinyl chloridepolymers, but also. to impart. simultaneously a high degree of low temperature flexibility, verygood temperature stability and great mechanical strength to these polymers. While manyof the esters encompassed by the Clocker patents referred, to above are-incompatible'with polymers and copolymers of vinyl chlorideand, do not give continuous, homogeneous compositions, thepresent esters .are compatible with vinyl chloridepolymers and show no exudation of plasticizer even at plasticizer content of up to 50 percent. Although-the quantity of plasticizer will depend] upon the particular polymer to be plasticized and upon its molecular weight, it isgenerally found that compositions having from 5 to SOpercent by weight of plasticizer will; in most cases, be satisfactory for general utility. The good flexibilityfof the plasticized compositions increases with increasing plasticizer-concentration.

The present esters are valuable plasticizers for poly vinyl chloride and copolymers of at. least 70 percent by weight of vinyl chloride and up to 30 percent by weight of an unsaturatedmonomer copolymerized therewith, for example,- vinyl acetate, vinylidene chloride, etc.

In evaluating plasticizer efliciency use is made of the following empirical testing procedures:

Cmpatibility.Visual inspection of the plasticized composition is employed, incompatibility of the plasticizer with the polymer being demonstrated by cloudiness and exudation of the plasticizer.

Hardness.-A standard instrument made by the Shore Instrument Company is used for this determination and expresses the hardness in units from one to 100. The hardness of a composition is judged by its resistance to the penetration of a standard needle applied to the composition under a standard load for a standard length of time.

Low temperature flexibility.Low temperature flexability is one of the most important properties of elastomeric vinyl compositions. While many plasticizers will produce flexible compositions at room temperature the flexibility of these compositions at low temperatures may vary considerably, i. e., plasticized polyvinyl chloride compositions that are flexible at room temperature often become very brittle and useless at low temperatures. Low temperature flexibility tests herein employed are according to the Clash-Berg method. This method determines the torsional flexibility of a plastic at various temperatures. The temperature at which the vinyl composition exhibits an arbitrarily established minimum flexibility is defined as the low temperature flexibilty of the composition. This value may also be defined as the lower temperature limit of the plasticized compositions usefulness as an elastomer.

Volatility.-Just as a decrease in low temperature often results in decreased flexibilty of a plasticized polymer composition so does a decrease in plasticizer concentration when caused by volatilization of the plasticizer. Hence, plasticizers which are readily volatilized from the plasticized composition as a result of aging or heating are ineflicient because upon volatilization the plasticized composition becomes stiff and hard. The test for plasticizer volatility herein employed is that described by the American Society for Testing Materials under the designation D74444T.

The invention is further by the following examples:

illustrated, but not limited,

Example I This example shows the preparation of tris(tetrahydrofurfuryl) (1,2'-dicarboxyethyl) octadecenoate.

A mixture consisting of 120.0 g. of the oleic acidmaleic anhydride Clocker adduct and 204.6 g. of tetrahydrofurfuryl alcohol and 30 ml. of benzene was refluxed in a flask which was equipped with a condenser and a Dean-Stark water-trap for a time of 12 hours. During this period the pot temperature increased from 110 C. up to 240 C. At the end of this time esterification was not quite complete; accordingly, there was added to the reaction mixture g. of p-toluenesulfonic acid as esterifying catalyst and 100 ml. of toluene as diluent. The resulting mixture was then heated for an additional 3.5 hours at a temperature of about 120 C. The product was then cooled, washed thoroughly with water, treated with ml. of 10 percent aqueous sodium hydroxide, and washed with water until neutral. Removal of the dilents from the product was then etfected by heating at a temperature of 220 C./1 mm. of mercury pressure. The residue was the substantially pure tris (tetrahydrofurfuryl)(1',2' biscarboxyethyl) octadecenoate, n 1.4806, having a free acid content of 0.635 percent.

Example 2 This example shows the preparation of tris(tetrahydrofurfuryl) 1,2'-dicarboxyethyl)undecylenate.

A mixture consisting of 70.6 g. (0.25 mole) of the lO-undecylenic acid-maleic anhydride adduct, 153.6 g. (1.5 moles) of tetrahydrofurfuryl alcohol, 3 g. of toluenesulfonic acid and ml. of benzene was refluxed for a time of 7.5 hours. A Dean-Stark water-trap was employed, and during this time there was collected 8.0 ml. of Water. The resulting product was then allowed to cool, washed neutral and then treated with 5 ml. of 10 percent aqueous sodium hydroxide. The water layer was separated and the residue was dried at a temperature of 100 C./ 18 mm. of mercury pressure. Removal of the diluent and unreacted material from the dried residue by distillation at a temperature of up to 230 C./1.0 mm. of mercury pressure gave 100 g. (72.6 percent yield) of the substantially pure tris(tetrahydrofurfuryl) (1',2-dicarboxyethyl)undecylenate, 11 1.4867, testing 0.47 percent free acid.

Example 3 Sixty parts of polyvinyl chloride and 40 parts by weight of the tris(tetrahydrofurfuryl) (l,2-dicarboxyethyl)octadecenoate are mixed on a rolling mill to a homogeneous blend. During the milling there was observed substan tially no fuming and discoloration. A molded sheet of the mixture was clear and transparent and substantially colorless. Testing of the molded sheet for low temperature flexibility, according to the testing procedure described above, gave a value of minus 14 C., which value denotes good low temperature properties. Tests on the volatility characteristics of the plasticized composition gave a value of 1.9 percent which showed extremely good retention of plasticizer and indicated good temperature characteristics of the composition. The plasticized material had a hardness of 78 before the volatility test and a hardness of 81 after the volatility test. When subjected to heat at a temperature of 325 F. for a period of 30 minutes the clarity and color of the molded sheet were substantially unchanged.

Example 4 Operating as in Example 3, but employing tris(tetrahydrofurfuryl) 1 ,2-dicarboxyethyl)undecylenate instead of the ester employed in Example 3, there was obtained a plasticized polyvinyl chloride composition having a low temperature flexibility value of minus 7 C. The tests on the volatility characteristics of the plasticized composition gave a value of 1.1 percent, which value shows very good retention of the plasticizer. The plasticized material had a hardness of 77 before the volatility test and a hardness of 77 after the volatility test. When subjected to heat as in Example 3, the color of the present molded product was substantially unchanged.

Instead of the ester employed in the examples above, other esters of Clocker adducts and tetrahydro'furfuryl alcohol give similarly valuable plasticized polyvinyl chloride compositions. Thus, by employing 40 parts by weight of the methyl, amyl, butyl, 2-ethylhexyl or ethyl [1,2' bis(carbotetrahydrofurfuryl)ethylJoctadecenoate or propyl, tert-butyl or n-octyl [1',2-bis(carbotetrahydrofurfuryl)ethyllundecylenate with 60 parts by weight of polyvinyl chloride or with 60 parts by weight of a vinyl chloride-vinyl acetate copolymer known to the trade as Vinylite, there may be obtained clear, colorless compositions of very good flexibility and stability.

While the above examples show only compositions in which the ratio of plasticizer to polymer content is 40:60, this ratio being employed in order to get comparable efliciencies, the content of ester to polyvinyl chloride may be widely varied, depending upon the properties desired in the final product. For many purposes a plasticizer content of, say, from only 10 percent to 20 percent is preferred. The present esters are compatible with polyvinyl chloride over wide ranges of concentrations, up to 50 percent of esters based on the total weight of the plasticized composition yielding desirable products.

Although the invention has been described particularly with reference to the use of the present esters of Clocker adducts and tetrahydrofurfuryl alcohol as plasticizers for polyvinyl chloride, these esters are advantageously employed also as plasticizers for copolymers of vinyl chloride, for example, the copolymers of vinyl chloride with vinyl acetate or vinylidene chloride, etc. Preferably such copolymers have a high vinyl chloride content, i. e., a vinyl chloride content of at least 70 percent by weight of vinyl chloride and up to 30 percent by weight of the copolymerizable monomer.

The plasticized polyvinyl halide compositions of the present invention have good thermal stability; however, for many purposes it may be advantageous to use known stabilizers in the plasticized compositions. Inasmuch as the present esters are substantially unreactive with the commercially available heat and light stabilizers which are commonly employed with polyvinyl chloride or copolymers thereof, the presence of such materials in the plasticized compositions does not impair the valuable properties of the present esters. The present esters are of general utility in softening vinyl chloride polymers. They may be used as the only plasticizing component in a compounded vinyl chloride polymer or they may be used in conjunction with other plasticizers.

This is a continuation-in-part of my application Serial No. 164,307, filed May 25, 1950, now Patent No. 2,757,180.

What I claim is:

A resinous composition comprising polyvinyl chloride plasticized with tris(tetrahydrofurfury1)(l',2'-dicarboxyethyl) octadecenoate.

References Cited in the file of this patent UNITED STATES PATENTS 2,510,915 Spurlin June 6, 1950 

